EP0384013A1

EP0384013A1 - Method for strengthening coldworked nickel-base alloys

Info

Publication number: EP0384013A1
Application number: EP89121674A
Authority: EP
Inventors: Jimmy Carroll England; Hugh Hiram Ruble, Jr.; Jon Michael Poole
Original assignee: Inco Alloys International Inc
Current assignee: Huntington Alloys Corp
Priority date: 1989-02-21
Filing date: 1989-11-23
Publication date: 1990-08-29
Also published as: CA2000383A1; JPH02228456A; US4909860A

Abstract

A heat-treatment method for strengthening cold-worked tubes and other articles made from nickel-base alloys without an attendant loss in corrosion resistance properties. The method is especially useful for tubes destined for energy resource recovery areas, oil fields, sour gas wells, etc., and the tubes may be heated from 316 to 769°C (600 to 1100°F) for up to an hour.

Description

The instant invention relates to nickel-base alloys in general and more particularly to a method for strengthening these alloys.
Oil country products, in particular articles and parts used in the oil and gas industry, are often subject to demanding conditions. In particular sour gas wells and certain oil fields contain highly corrosive agents that when combined with the elevated temperatures present wreak havoc with metallic members.
Accordingly, nickel-base alloys have been repeatedly selected for these demanding applications.
For example, INCO alloys G-3 and C-276 and INCOLOY alloy 825 (INCO and INCOLOY are trademarks of the applicant company) have been specified for use in deep sour gas wells and also for seamless pipes and liners in oil fields. For these applications the materials must meet stringent specifications dictating the acceptable range of room temperature tensile properties, hardness, macrostructure, microstructure and corrosion properties. Of particular interest to the energy companies is the room temperature 0.2% yield strength which is usually restricted to narrow ranges (e.g. 758 to 896 MPa [110 to 130 ksi], 862 to 1000 MPa [125 to 145 ksi], 896 to 1034 MPa [130 to 150 ksi]).
INCO alloy G-3 is a nickel-chromium-iron alloy with additions of molybdenum and copper. It has good weldability and resistance to intergranular corrosion in the welded condition. The low carbon content helps prevent sensitisation and consequent intergranular corrosion of weld heat-affected zones. It is most useful in corrosive environments. The nominal composition of alloy G-3 is about 21 to 23.5% chromium, 18 to 21% iron, 6 to 8% molybdenum, up to 5% cobalt, 1.5 to 2.5% copper, up to 1.5% tungsten, up to 1% silicon, up to 1% manganese, balance nickel, and traces of other elements.
INCO alloy C-276 is a nickel-molybdenum-chromium alloy with an addition of tungsten having excellent corrosion resistance in a wide range of severe environments. The molybdenum content makes the alloy especially resistant to pitting and crevice corrosion. The low carbon content minimises carbide precipitation during welding to maintain corrosion resistance in as-welded structures. The nominal composition is about 15 to 17% molybdenum, 14.5 to 16.5% chromium, 4 to 7% iron, 3 to 4.5% tungsten, up to 2.5% cobalt, up to 1.0% manganese, balance nickel, and traces of other elements.
INCOLOY alloy 825 is a nickel-iron-chromium alloy with additions of molybdenum and copper. It has excellent resistance to both reducing and oxidizing acids, to stress corrosion cracking and to localised attack such as pitting and crevice corrosion. The nominal composition is about 19.5 to 23.5% chromium, 38 to 46% nickel, 2.5 to 3.5% molybdenum, 1.5 to 3% copper, 0.6 to 1.2% titanium, up to 1% manganese, at least 22% iron and traces of other elements.
Trace elements referred to herein may include impurities and residual deoxidation and treatment elements.
Alloy 825, having an appreciable quantity of iron, has been heat-treated by the applicant company in the past to strengthen tubes. By inserting the finally reduced tube into a salt bath having a temperature of about 482°C (900°F) for about one half-hour, the resultant room temperature yield strength and tensile strength improved, on average, about 5% and 7% respectively given an initial 150 ksi (1034 MPa) tensile strength and 130 ksi (896 MPa) yield strength.
There are differences in alloy G-3 and alloy 825 that do not permit straight expected comparisons. Besides different chemistries, alloy 825 forms an M₂₃C₆ phase, whereas alloy G-3 forms a (Ni,Cr,Fe,Co)₃ (Mo,W)₂ u (mu) phase. These phase and chemistry differences result in different corrosion and work hardening behaviours.
A typical processing route for the manufacture of oil and gas field pipe is to produce a billet, extrude the billet to a tube, solution-anneal the tube, reduce the tube, solution-anneal the tube and subject the tube to a final tube reduction. The final tube reduction is performed with a controlled level of cold work to attain the desired yield strength. See Fig. 1 (solid lines). Unfortunately, for the alloys a prohibitively high level of cold work is necessary to reach the desired high-yield strength levels. To overcome this limitation the annealing temperature can be reduced, as the material's strength will increase as the anneal temperature decreases at a fixed level of cold work. However, this practice is limited by:

(1) the precipitation of undesirable phases formed at lower temperatures;
(2) the reduction of the material's corrosion resistance; and
(3) in some cases the reduction of room temperature ductility.

Hence, it is desirable to define a processing method to increase the material's strength without sacrificing the other properties, in particular, corrosion resistance.
Accordingly, a strengthening method is provided that does not result in a loss in ductility or corrosion resistance. A 316 to 769°C (600 to 1100°F) heat treatment after the final cold working operation is conducted for up to about an hour.
In the accompanying drawings:

Fig. 1 is a work hardening curve plotting 0.2% yield strength against percent cold work for the solution annealed alloys;
Fig. 2 is a graph plotting room temperature tensile strength of one alloy against exposure temperature; and
Fig. 3 is a graph plotting room temperature yield strength against exposure temperature for the same alloy.

As alluded to above, tubes for oil and gas pipe may be made by producing a billet, extruding the billet to a tube, solution-annealing the tube, reducing the tube, solution-annealing the tube and finally reducing the tube to the desired diameter and wall thickness. The final reduction step puts cold work into the tube finalising the physical and chemical properties of the tube.
The strength of the tube may be enhanced without a significant loss in ductility or corrosion resistance. For nickel-base alloys having iron levels below about 22% this may be easily accomplished by generally employing a 316 to 769°C (600 to 1100°F) thermal treatment after the final cold working operation. See Figs. 2 and 3. These two Figures show the effect of exposure temperature on the room temperature tensile properties of alloy G-3.
The observed strength increase can range from about 0 to 207 MPa (0 to 30 ksi) with the magnitude of the increase dependent on the final cold reduction. It is generally independent of the exposure time, which can run from about fifteen minutes to one hour. The strengthening heat treatment may be accomplished with standard means furnace, molten bath, etc.
More particularly, it is preferred to treat a cold-worked tube made from a nickel-base alloy having an iron content less than about 22%, such as say alloy G-3, at about 482°C (900°F) to 510°C (950°F) for up to about 30 minutes. The resultant tube displays increased strength, vis-à-vis a similar non-treated cold-worked tube, yet it retains the desired corrosion-resistant characteristics. From experience with salt baths, a 482°C (900°F) heat treatment is most satisfactory.
Although the inventors do not wish to be bound to the following explanation, the mechanism accounting for the strength increase is believed to be strain ageing. This is a phenomenon where the solute atoms (Mo, W or C, N) segregate to the high-energy dislocation positions in the alloy and restrict their movement (solute atmosphere). The macro effect is an observed strength increase. Further, since the Mo and W or C and N segregation is on an atomic scale and is in an uncombined form, this phenomenon does not invoke depletion of Mo and W or C and N which normally leads to a degradation in corrosion resistance. Hence, the material's strength is enhanced without loss in corrosion resistance and with moderate cold work levels (generally above 20% cold work). This is illustrated by the broken line curve in Fig. 1. Alloy C-276 is shown for comparison purposes.
While the invention is illustrated and described herein with reference to specific embodiments, those skilled in the art will understand that changes may be made in the form of the invention and that certain features of the invention may sometimes be used to advantage without a corresponding use of the other features.

Claims

1. A method of increasing the strength of a cold-worked, corrosion-resistant article of manufacture of a metal-base alloy containing less than about 22% iron which comprises subjecting the article to a post-cold-work heat treatment in the temperature range of about 316 to 769°C (600 to 1100°F) for from about five minutes to about one hour.

2. A method according to claim 1 wherein the article is heat-treated at about 482 to 510°C (900 to 950°F).

3. A method according to claim 1 or claim 2 wherein the article is heat-treated at about 482°C (900°F) for up to about one half-hour.

4. A method according to any preceding claim wherein the article contains about 21 to 23.5% chromium, 18 to 21% iron, 6 to 8% molybdenum, up to 5% cobalt, 1.5 to 2.5% copper, up to 1.5% tungsten, up to 1% silicon, up to 1% manganese, balance nickel, and traces of other elements.

5. A method according to any preceding claim wherein the article is a tube and the method that includes the steps of producing a billet, forming a tube from the billet, thermally treating the tube, cold-working the tube to predetermined dimensions, and subjecting the tube to the said post-cold-work heat treatment.